In-situ XANES experiments on Ni K-edge in mesoporous ZrO2-CeO2:Ni.

Ordered mesoporous ZrO2-CeO2 mixed oxides are potential candidates for catalytic applications. These systems, used as anodes in solid oxide fuel cells (SOFC), may lead to better performance of SOFCs, due to an enhancement on surface area, aiming to achieve a lower working temperature. The aim of this studies is to evaluate the reduction capacity of Ni2+ to Ni in ZrO2-x(mol)%CeO2 (x=50 and 90) samples impregnated with 60(wt.)%NiO. The synthesis was made with Zr and Ce chloride precursors, HCl aqueous solution, Pluronic P123, NH4OH to adjust the pH (3-4) and a teflon autoclave to perform a hydrothermal treatment (80oC/48h). The samples were dried and calcined, until 540oC in N2 and 4 hours in air. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)£6H2O. The powder was calcinated in air until 350oC for 2 hours. Temperature-resolved XANES data at the Ni K-edge were collected at the DXAS beam line of the LNLS in transmission mode, using a Si(111) monochromator and a CCD detector. Sample preparation consisted of mixing »6mg of the powder samples with boron nitride and pressing into pellets. The data were acquired during an experiment of temperature programmed reduction (TPR) under a 5% H2/He until 600oC and mixtures of 20%CH4:5%O2/He, at temperatures from 400 to 600oC. All the reactions were monitored with a mass spectrometer. The data was analyzed with a linear combination fit of 2 standards for each valence number using Athena software. The Ni K-edge experiments demonstrated that for both contents of CeO2, NiO embedded in the porous zirconia-ceria matrix reduces at lower temperatures than pure NiO, revealing that the ZrO2-CeO2 support improves the reduction of impregnated NiO. Ni was oxidized to NiO after all reactions with methane and oxygen. Hydrogenated carbonaceous species were detected, but under reducing conditions, the hydrocarbon compounds are removed. The reaction of total oxidation of methane CH4:O2 (1:2 ratio) was observed at lower temperatures (around 400oC) for both samples.

Structural XANES characterization of Ca0.99Sm0.01TiO3 perovskite and correlation with photoluminescence emission

In this work, CaTiO3:Sm (CT:Sm) were prepared by a soft chemical processing at different annealing temperatures starting with a disordered structure and reaching an ordered one, with the propose to understand the relationship between structural order-disorder and photoluminescence emission. The samples were characterized by titanium K-edge, Titanium L-II and L-III-edge XANES, electron paramagnetic resonance (EPR) and photoluminescence (PL) measurements. XANES results clearly point the presence of local distortion in [TiO6] octahedral clusters until the crystallization was completed. The interactions of the network clusters that form the CT:Sm structures provides favorable structural and electronic conditions for the appearance of PL phenomena. (C) 2012 Published by Elsevier B.V.

Local order and electronic structure of Pb1-xLaxZr0.40Ti0.60O3 materials and its relation with ferroelectric properties

The knowledge of electronic and local structures is a fundamental step towards understanding the properties of ferroelectric ceramics. X-ray absorption near-edge structure (XANES) of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric samples was measured in order to know how the local order and electronic structure are related to their ferroelectric property, which was tailored by the substitution of lead by lanthanum atoms. The analysis of XANES spectra collected at Ti K- and L-edges XANES showed that the substitution of Pb by La leads to a decrement of local distortion around Ti atoms on the TiO6 octahedron. The analysis of O K-edge XANES spectra showed that the hybridization between O 2p and Pb 6sp states is related to the displacement of Ti atoms in the TiO6 octahedra. Based on these results, it is possible to determine that the degree of ferroelectricity in these samples and the manifestation of relaxor behavior are directly related to the weakening of O 2p and Pb 6sp hybridization. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720472]

Biogenic calcium phosphate transformation in soils over millennial time scales

Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, beta-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

Optimization of x-ray spectra in digital mammography through Monte Carlo simulations

In this work, a Monte Carlo code was used to investigate the performance of different x-ray spectra in digital mammography, through a figure of merit (FOM), defined as FOM = CNR2/(D) over bar (g), with CNR being the contrast-to-noise ratio in image and (D) over bar (g) being the average glandular dose. The FOM was studied for breasts with different thicknesses t (2 cm <= t <= 8 cm) and glandular contents (25%, 50% and 75% glandularity). The anode/filter combinations evaluated were those traditionally employed in mammography (Mo/Mo, Mo/Rh, Rh/Rh), and a W anode combined with Al or K-edge filters (Zr, Mo, Rh, Pd, Ag, Cd, Sn), for tube potentials between 22 and 34 kVp. Results show that the W anode combined with K-edge filters provides higher values of FOM for all breast thicknesses investigated. Nevertheless, the most suitable filter and tube potential depend on the breast thickness, and for t >= 6 cm, they also depend on breast glandularity. Particularly for thick and dense breasts, a W anode combined with K-edge filters can greatly improve the digital technique, with the values of FOM up to 200% greater than that obtained with the anode/filter combinations and tube potentials traditionally employed in mammography. For breasts with t < 4 cm, a general good performance was obtained with the W anode combined with 60 mu m of the Mo filter at 24-25 kVp, while 60 mu m of the Pd filter provided a general good performance at 24-26 kVp for t = 4 cm, and at 28-30 and 29-31 kVp for t = 6 and 8 cm, respectively.

Photoluminescence in silicon/silicon oxide films produced by the Pulsed Electron Beam Ablation technique

In this work we report studies of the photoluminescence emission in samples based on Si/SiOx films deposited by the Pulsed Electron Beam Ablation (PEBA) technique. The samples were prepared at room temperature using targets with different Si/SiO2 concentrations. The samples were characterized using X-ray Absorption Edge Spectroscopy (XANES) at the Si-K edge, Raman spectroscopy, Photoluminescence (PL) and X-ray Photoelectron Spectroscopy (XPS). The concentration of a-Si and nc-Si in the film was dependent on the silicon concentration in the target. It was also observed that the PL is strongly dependent on the structural amorphous/crystalline arrangement. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Distribution of major elements in Atlantic surface sediments (36 degrees N-49 degrees S): Imprint of terrigenous input and continental weathering

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36 degrees N-49 degrees S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e. g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

We report herein for the first time a facile synthesis method to obtain SrTi1-xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 degrees C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (E-gap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.

Radiative association of Ti and O atoms

Rate coefficients for the radiative association of titanium and oxygen atoms to form the titanium monoxide (TiO) molecule are estimated. The radiative association of Ti(F-3) and O(P-3) atoms is dominated by an approach along the C-3 Delta potential energy curve, accompanied by spontaneous emission into the X-3 Delta ground state of TiO. For temperatures ranging from 300-14 000 K, the total rate coefficients are found to vary from 4.76 x 10(-17) to 9.96 x 10(-17) cm(3) s(-1), respectively.

On the electrical conductivity of Ti-implanted alumina

Ion implantation of metal species into insulators provides a tool for the formation of thin, electrically conducting, surface layers with experimenter-controlled resistivity. High energy implantation of Pt and Ti into alumina accelerator components has been successfully employed to control high voltage surface breakdown in a number of cases. In the work described here we have carried out some basic investigations related to the origin of this phenomenon. By comparison of the results of alumina implanted with Ti at 75 keV with the results of prior investigations of polymers implanted with Pt at 49 eV and Au at 67 eV, we describe a physical model of the effect based on percolation theory and estimate the percolation parameters for the Ti-alumina composite. We estimate that the percolation dose threshold is about 4 x 10(16) cm(-2) and the maximum dose for which the system remains an insulator-conductor composite is about 10 x 10(16) cm(-2). The saturation electrical conductivity is estimated to be about 50 S/m. We conclude that the observed electrical conductivity properties of Ti-implanted alumina can be satisfactorily described by percolation theory. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3697900]

Edge Colourings of Graphs Avoiding Monochromatic Matchings of a Given Size

Let k and l be positive integers. With a graph G, we associate the quantity c(k,l)(G), the number of k-colourings of the edge set of G with no monochromatic matching of size l. Consider the function c(k,l) : N --> N given by c(k,l)(n) = max {c(k,l)(G): vertical bar V(G)vertical bar = n}, the maximum of c(k,l)(G) over all graphs G on n vertices. In this paper, we determine c(k,l)(n) and the corresponding extremal graphs for all large n and all fixed values of k and l.

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy by mechanical spectroscopy

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy were obtained using the mechanical spectroscopy technique. The sample with heat treatment at 1170K for 30 minutes and water quenched with subsequent aging treatment at 670 K for 3 hours (TNZ + WQ + 670 K/3 h), was characterized through decay of free oscillations of the sample in the flexural vibration mode. The spectra of anelastic relaxation (internal friction and frequency) in the temperature range from 300 K to 625 K not revealed the presence of relaxation process. As shown in the literature, the hcp structure usually does not exhibit any relaxation due to the symmetry of the sites in the crystalline lattice, but if there is some relaxation, this only occurs in special cases such as low concentration of zirconium or saturation of the stoichiometric ratio of oxygen for zirconium. Dynamical elastic modulus obtained for TNZ + WQ + 670 K/3 h alloy was 87 GPa at room temperature, which is higher than the value for Ti-13Nb-13Zr alloy (64 GPa) of the literature. This increment may be related to the change of the proportion of α and β phases. Besides that, the presence of precipitates in the alloy after aging treatment hardens the material and reduces its ductility.